CN105779939A - Preparation method of p type copper oxide thin film with low resistivity and high carrier concentration - Google Patents
Preparation method of p type copper oxide thin film with low resistivity and high carrier concentration Download PDFInfo
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- CN105779939A CN105779939A CN201610171960.3A CN201610171960A CN105779939A CN 105779939 A CN105779939 A CN 105779939A CN 201610171960 A CN201610171960 A CN 201610171960A CN 105779939 A CN105779939 A CN 105779939A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/087—Oxides of copper or solid solutions thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
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Abstract
The invention discloses a preparation method for a p type copper oxide thin film with low resistivity and high carrier concentration. The method comprises the step of selecting lithium-doped copper oxide as a target for pulsed laser deposition by selecting a proper lithium doping concentration to obtain the p type copper oxide thin film with low resistivity and high carrier concentration, wherein when the doping amount of metal lithium is 2wt%, the resistivity of the obtained p type copper oxide thin film is 7.56 omega.cm, and the carrier concentration is 7.39*10<19>/cm<3>. The preparation method disclosed by the invention is simple to operate and suitable for industrial preparation of the p type copper oxide thin film with low resistivity and high carrier concentration.
Description
Technical field
The invention belongs to semiconductor film material preparing technical field, be specifically related to a kind of low-resistivity, high carrier
The preparation method of the p-type CuO film of concentration.
Background technology
Cupric oxide is a kind of important semi-conducting material, and its optical energy gap is 1.2eV～1.9eV.With the sun
Energy spectrum is close, thus has preferable absorbability to sunshine, and its theoretical conversion efficiency is 31%, thus is one
Plant ideal solar cell material.And the most natural cupric oxide is shown as p-type conductivity,
This is the existence in the room due to intrinsic defect copper.Have substantial amounts of copper resource on earth, thus cupric oxide has
The feature that cheap, preparation cost is relatively low so that it is become a kind of material with extensive use.In solar-electricity
The aspects such as pond, photochemical catalyst, electrode material, resistance-variable storing device, superconductor, hydrogen manufacturing, photochromic have the strongest
Application.But owing to the resistivity of CuO film material is higher, carrier concentration is relatively low, thus have impact on oxidation
Copper electronics and the performance of opto-electronic device.Therefore, the side of the p-type CuO film of the electric property prepared is sought
Method is extremely important.
Summary of the invention
The technical problem to be solved is to provide a kind of simple to operate, and resistivity is low, carrier concentration is high
The preparation method of p-type CuO film.
Solve above-mentioned technical problem to be the technical scheme is that substrate and the cupric oxide of doping 1wt%～4wt% lithium
The settling chamber of pulsed laser deposition equipment put into by target, and settling chamber is evacuated to 1 × 10-3Below Pa, heating lining
Oxygen ventilation valve, to 450～550 DEG C, is opened in the end, is passed through oxygen to settling chamber, the pressure of regulation settling chamber be 8～
12Pa, then with KrF excimer pulsed laser bombardment oxidation copper target, deposited oxide Copper thin film on substrate, arteries and veins
The frequency of impulse light is 3～8Hz, and sedimentation time is 1～2 hour, after deposition terminates, naturally cools to room temperature,
Obtain p-type CuO film.
The oxidation copper target of substrate and doping 2wt% lithium is further preferably put into pulsed laser deposition equipment by the present invention
In settling chamber, settling chamber is evacuated to 1 × 10-4Below Pa, heating substrate, to 500 DEG C, opens oxygen ventilation
Valve, is passed through oxygen to settling chamber, and the pressure of regulation settling chamber is 8Pa, then bangs with KrF excimer pulsed laser
Hitting oxidation copper target, deposited oxide Copper thin film on substrate, the frequency of pulse laser is 5Hz, and sedimentation time is 2
Hour, after deposition terminates, naturally cool to room temperature, obtain p-type CuO film
Above-mentioned substrate is 4～8cm with the distance of oxidation copper target；The energy model of described pulse laser is permanent energy
Pattern, laser energy density is 150mJ/Plus；Described substrate is monocrystalline silicon piece, simple glass, quartz glass
Any one in glass, indium tin oxide-coated glass, fluorine doped tin oxide electro-conductive glass.
The present invention uses pulsed laser deposition, by the doping of lithium metal, forms p-type cupric oxide thin on substrate
Film.The present invention is simple to operate, and the p-type CuO film resistivity obtained is low, carrier concentration is high, wherein metal
When the doping of lithium is 2wt%, the resistivity of the p-type CuO film obtained is 7.56 Ω cm, carrier concentration
It is 7.39 × 1019cm-3。
Accompanying drawing explanation
Fig. 1 is embodiment 1～3 and the X-ray diffractogram of p-type CuO film of comparative example 1 preparation.
Fig. 2 is embodiment 1～3 and the transmitted spectrum figure of p-type CuO film of comparative example 1 preparation.
Fig. 3 is embodiment 1～3 and the optical band gap figure of p-type CuO film of comparative example 1 preparation.
Detailed description of the invention
The present invention is described in more detail with embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention not only limits
In these embodiments.
Embodiment 1
Ultrasonic cleaning 5 minutes in acetone, ethanol, deionized water successively by common glass substrate, dry up with nitrogen.
Weigh 0.98g cupric oxide powder and 0.02g lithium metal powder, be put in the metal die of a diameter of 2cm by pressure
Target pressed under pressure is 10MPa by sheet machine, obtains the oxidation copper target of doping 1wt% lithium.The common glass that will clean up
The oxidation copper target of glass substrate and doping 2wt% lithium is sent in the settling chamber of pulsed laser deposition equipment by manipulator,
With mechanical pump and molecular pump, settling chamber is evacuated to 1 × 10-4Pa, regulation glass substrate and the distance of oxidation copper target
For 6cm, then glass substrate is heated to 500 DEG C, then opens oxygen ventilation valve, be passed through oxygen to settling chamber
Gas, and open mass flowmenter, control oxygen flow is 18sccm, regulation settling chamber pressure to 8Pa.Use ripple
The KrF excimer pulsed laser of a length of 248nm carries out optical path adjusting under energy density is 50mJ/Plus, will
Hot spot focuses in the oxidation copper target of doping 1wt% lithium, then swashs with the KrF excimer pulse that wavelength is 248nm
Light is practiced shooting under energy density is 150mJ/Plus, and rotary target material and substrate simultaneously, deposits on a glass substrate
CuO film, the frequency of pulse laser is 5Hz, and energy model is permanent energy pattern, and sedimentation time is 2 hours,
After deposition terminates, naturally cool to room temperature, obtain the p-type CuO film that thickness is 230nm.
Comparative example 1
In embodiment 1, the oxidation copper target of doping 2wt% lithium, other steps and enforcement are replaced by pure oxidation copper target
Example 1 is identical, obtains p-type CuO film.
Embodiment 2
In embodiment 1, replace the oxidation copper target of doping 2wt% lithium by the oxidation copper target of doping 1wt% lithium, other
Step is same as in Example 1, obtains p-type CuO film.
Embodiment 3
In embodiment 1, replace the oxidation copper target of doping 2wt% lithium by the oxidation copper target of doping 4wt% lithium, other
Step is same as in Example 1, obtains p-type CuO film.
Inventor uses x-ray diffractometer, UV, visible light near infrared spectrometer, Hall effect tester to embodiment
1～3 and comparative example 1 preparation p-type CuO film characterize, result is shown in Fig. 1～3 and table 1.
Table 1 embodiment 1～3 and the electric property of p-type CuO film of comparative example 1 preparation
As seen from Figure 1, embodiment 1～3 and the p-type CuO film of comparative example 1 preparation all occur in that CuO (002)
(111) diffraction maximum of crystal face, but the p-type CuO film prepared relative to comparative example 1 undoped p lithium, real
The diffraction maximum of p-type CuO film (111) crystal face executing example 1～3 preparation gradually increases along with the increase of lithium doping amount
By force, illustrate that elements doped lithium can promote the oriented growth of CuO (111) crystal face, the growth of suppression (002) crystal face.
From Fig. 2～3, the optical band gap of the p-type CuO film of embodiment 1～3 and comparative example 1 preparation divides
Not Wei 1.46eV, 1.42eV, 1.52eV, 1.50eV, illustrate elements doped lithium to preparation p-type CuO film
Optical band gap impact little.
From table 1, compared with comparative example 1, embodiment 1～3 uses p prepared by the oxidation copper target of elements doped lithium
The resistivity of type CuO film substantially reduces, carrier concentration significantly increases, the cupric oxide of the 2wt% lithium that wherein adulterates
The electric property of p-type CuO film prepared by target is best, and its resistivity reduces about 66 relative to comparative example 1
Times, carrier concentration improves about 30000 times relative to comparative example 1.Above-mentioned result of the test illustrates, side of the present invention
Method can significantly improve the electric property of p-type CuO film.
Claims (5)
1. the preparation method of the p-type CuO film of a low-resistivity, high carrier concentration, it is characterised in that:
The oxidation copper target of substrate and doping 1wt%～4wt% lithium is put into the settling chamber of pulsed laser deposition equipment, will deposition
Room is evacuated to 1 × 10-3Below Pa, heating substrate, to 400～550 DEG C, opens oxygen ventilation valve, to deposition
Room is passed through oxygen, and the pressure of regulation settling chamber is 8～12Pa, then with the bombardment oxidation of KrF excimer pulsed laser
Copper target, deposited oxide Copper thin film on substrate, the frequency of pulse laser is 3～8Hz, and sedimentation time is 1～2
Hour, after deposition terminates, naturally cool to room temperature, obtain p-type CuO film.
Low-resistivity the most according to claim 1, the preparation of p-type CuO film of high carrier concentration
Method, it is characterised in that: the oxidation copper target of substrate and doping 2wt% lithium is put into the deposition of pulsed laser deposition equipment
Indoor, are evacuated to 1 × 10 by settling chamber-4Below Pa, heating substrate to 500 DEG C, open oxygen ventilation valve,
Be passed through oxygen to settling chamber, the pressure of regulation settling chamber is 8Pa, then bombards oxygen with KrF excimer pulsed laser
Changing copper target, deposited oxide Copper thin film on substrate, the frequency of pulse laser is 5Hz, and sedimentation time is 2 hours,
After deposition terminates, naturally cool to room temperature, obtain p-type CuO film.
Low-resistivity the most according to claim 1 and 2, the p-type CuO film of high carrier concentration
Preparation method, it is characterised in that: described substrate is 4～8cm with the distance of oxidation copper target.
Low-resistivity the most according to claim 1 and 2, the p-type CuO film of high carrier concentration
Preparation method, it is characterised in that: the energy model of described pulse laser is permanent energy pattern, and laser energy density is
150mJ/Plus。
Low-resistivity the most according to claim 1, the preparation of p-type CuO film of high carrier concentration
Method, it is characterised in that: described substrate is monocrystalline silicon piece, simple glass, quartz glass, tin indium oxide conduction
Any one in glass, fluorine doped tin oxide electro-conductive glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610171960.3A CN105779939B (en) | 2016-03-24 | 2016-03-24 | A kind of low-resistivity, high carrier concentration p-type CuO film preparation method |
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|---|---|---|---|
| CN201610171960.3A CN105779939B (en) | 2016-03-24 | 2016-03-24 | A kind of low-resistivity, high carrier concentration p-type CuO film preparation method |
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| CN105779939A true CN105779939A (en) | 2016-07-20 |
| CN105779939B CN105779939B (en) | 2018-09-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756831A (en) * | 2016-12-27 | 2017-05-31 | 苏州思创源博电子科技有限公司 | A kind of preparation method of cupric oxide semiconductive thin film |
| CN107988629A (en) * | 2017-11-30 | 2018-05-04 | 山东大学 | A kind of preparation method of low resistivity p-type cuprous oxide epitaxial film |
| CN114875380A (en) * | 2022-05-05 | 2022-08-09 | 厦门理工学院 | Method for improving mobility of p-type oxygen-containing metal compound film |
-
2016
- 2016-03-24 CN CN201610171960.3A patent/CN105779939B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| PRAKASH CHAND，ET. AL: "Structural and optical study of Li doped CuO thin films on Si (100)substrate deposited by pulsed laser deposition", 《APPLIEDSURFACESCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756831A (en) * | 2016-12-27 | 2017-05-31 | 苏州思创源博电子科技有限公司 | A kind of preparation method of cupric oxide semiconductive thin film |
| CN107988629A (en) * | 2017-11-30 | 2018-05-04 | 山东大学 | A kind of preparation method of low resistivity p-type cuprous oxide epitaxial film |
| CN114875380A (en) * | 2022-05-05 | 2022-08-09 | 厦门理工学院 | Method for improving mobility of p-type oxygen-containing metal compound film |
| CN114875380B (en) * | 2022-05-05 | 2023-05-23 | 厦门理工学院 | Method for improving mobility of p-type oxygen-containing metal compound film |
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| CN105779939B (en) | 2018-09-25 |
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Granted publication date: 20180925 |